Effect of Mn doping on the electronic and optical properties of Dy₂Ti₂O₇: a combined spectroscopic and theoretical study

Abstract

Electronic and optical studies on Dy2Ti2−xMnxO7 (x = 0.00, 0.05, 0.10, 0.15, & 0.20) has been presented through both, theoretical (density functional theory calculations) and experimental (ultraviolet-visible absorption and photoluminescence emission spectroscopy) approaches. Density functional theory (DFT) calculations were employed considering the local density approximation (LDA) and LDA-1/2 for exchange-correlation interactions. Computed crystallographic parameters and energy band-gap using theoretical formulations are in good agreement with experimental results. The band-gap value obtained through the LDA-1/2 approach indicates insulated ground state of Dy2Ti2−xMnxO7 (x = 0.00, 0.05, 0.10, 0.15, 0.20) system. Experimentally obtained band gap value reduces from 3.82 eV to 2.45 eV with increase in positive chemical pressure as x increases from 0 to 0.20. Reduction in band gap value is attributed to the fact that there exists a lack of hybridization between the O-2p orbital and Ti-3d orbital, which is well corelated with the crystallographic data. Jahn-Teller effect is likely to be responsible for the presence of a mixed state of Mn (explained using x-ray photoelectron spectroscopy results), resulting in the intermediate Mn state between the valence band (VB) and the conduction band (CB) with immediate inclusion of Mn at Ti site in Dy2Ti2−xMnxO7 system.